Oil-modified resin compositions



Patented Dec. 31, 1946 'OIL-MODIFIED RESIN COMPOSITIONS I Arthur P.Mazzucchelll, Bloomfield, N. J assignor to Bakelite Corporation, acorporation of New Jersey No Drawing. Application May 19,1942,

Y Serial No. 443,643 a Claims- (C1. 260--19) This invention relates tocompositions of phenol aldehyde resins modified by the incorporation offatty oils and to their manufacture.

In a copending application Serial No. 351,217 filed August 3, 1940,which has since issued as U. S. Patent No. 2,362,018, there aredescribed and claimed fatty oil-containing resinous compositions whichare suitable as binders in dry processed molding material. According tothat application resinous compositions are prepared by reacting adehydrated Novolak type or slowly heat-hardening phenol aldehyde resin(using from 0.575 to 0.81 mol of formaldehyde to each mol'of phenol)with a fatty oil in amount up to 60 per cent by weight of the resin andthen incorporating from 2 to per cent of a hardening agent to make thecomposition rapidly thermosetting upon the application of heat; tosatisfactorily incorporate the fatty oil in the resin, it is necessaryto adjust the pH value of the reacted phenol formaldehyde resin tobetween 2.3 and about 8.25 in correspondence to the amount offormaldehyde reacted into the resin, the higher formaldehyde resinsbeing preferably adjusted to the upper pH value- It is further statedtherein that the reaction with a resin having a pH value below 3.0 issensitive to changes in operating conditions and increasingly difficultto control especially when the higher amounts of formaldehyde areemployed, although a high formaldehyde .ratio resin is desirable forspeed of cure; conversely when lower ratios of formaldehyde areemployed, the process is more readily operable at the lower pH valuesand favors the incorporation of fatty oils. In that application it isexplained that the oil-resin reaction may proceed in three differentdirections: (a) polymerization sary; material economies in the amount ofheatand time required for the manufacturing process are thus madepossible. Also fatty oils which are otherwise particularly difficult tosolubilize in Novolak type resins, such as the high viscosity fatty oilsproduced by heat-polymerization under vacuum or oils of lowunsaturation, can be incorporated substantially with the speed of themore easily dispersed blown oils. In addition Novolak type resinscontaining a high ratio of reacted formaldehyde are by this means mademore amenable to the incorporation of fatty oils.

When mineral acids are employed, the amount required to catalyze theincorporation of a fatty oil into a Novolak type resin is usually about4 per cent or less of the weight of the resin; above this amount eitherthe resin or the fatty oil or both tend to gel before a completedispersion has occurred, for acids generally have the property ofgelling the fatty oils and the Novolak type resins. In an acid-catalyzedoil-resin mass the temperature also becomes critical;'high temperatures(above 215 C.) promote rapidity of gelation with before the entire massbecomes a useless cloudy gelled mixture.

The invention is more fully set forth in the examples which follow, butit is to be understood that these examples are merely illustrative ofhow the invention may be practiced with varying proportions and kinds ofreactants. The proportions are by weight unless otherwise stated.

Example 1.-A Novolak type resin was made by reacting 5000 parts ofphenol containing 10 per cent of ortho cresol with 2750 parts of 37 percent aqueous formaldehyde and with 50 parts of per cent phosphoric acidas a catalyst. The mixture of these ingredients was refluxed at.atmospheric pressure with continuous mechanical agitation for about sixhours, when upon testing it was found thatv practically all theformaldehyde had reacted in and the pH -value of the mass as determinedby the separate'aqueous layer was 1.6; the resin was then dehydrated byheating to a temp rature of 160 C. under atmospheric pressure, resultingin a yield of 5180 parts of a resin having a melting point of 74 C.(ball and ring method). This Novolak resin was used as a base resin forincorporation with a fatty oil.

Example 1a.--1000 parts of the base Novolak resin of the precedingexample were melted in a steam heated vessel, and 20 parts ofconcentrated sulphuric acid previously dissolved in 40 parts of ethylalcohol to facilitate rapid dispersion were then added with agitation.Heating was continued until the temperature rose to 160 C. Then underconstant stirring 208 parts of raw soya bean oil were added in such amanner that the temperature of the reaction mass was maintained above130 C. When all the oil had been added the temperature was raised to 0.,and

at the end of -30 minutes the oil was found to be completelyincorporated in the resin as evidenced by a bead on a, plate which whenCooled to room temperature remained clear, The resin mass was subjectedto an additional half hour of heating at the same temperature under 28inches of vacuum to remove remainin volatile material and thenimmediately discharged into pans to cool. The oil-modified resin wasbrittle and grindable to give a non-sintering powder at room temperatureand had a melting point of 93 C.

Example 1b.The same conditions were followed as in the preceding ExampleIn but without added acid. 1000 parts of the base Novolal; resin weremelted and held at 160 C. in a steam heated vessel. To the melted resinwere added 208 parts of raw soya bean oil with constant stirring; themass was held at 165-170 C. until the resin gave a clear bead on coolingto room temperature. The reaction mass required about hours of heatingbefore this test was passed, after which it was heated to 170 C. andbodied under a vacuum of 28 inches so that the resinous mass would bebrittle at room temperature; this step required an additional 20 hours,and produced an oil-modified resin having a melting point of 86 C.

Example 1c.To show the effects of high temperature, 1000 parts of thebase Novolak resin and 208 grams of raw soya bean oil were heated to290-300 C. with continuous stirring in a gasflred vessel. The oildissolved readily within a few minutes in the resin at this hightemperature; but when an attempt was made to remove volatile matterunder vacuum, the viscosity of the mass increased so rapidly that beforeit could be removed from the vessel it had gelled.

To prevent the gelling at high temperature, the example was repeatedwith the residual phosphoric acid catalyst in the Novolak resinneutralized to the extent of about 80 per cent by adding to the samequantity of melted resin 2.25 parts of barium hydroxide, Ba(OH) 2-8H2O,dissolved in hot water; the pH value of the resin-water mixture was thusincreased to 3.8. The resin was then heated to expel the water afterwhich 208 parts of raw soya bean oil were added, and the mass was heatedto 300 C. and held at this temperature with constant stirring until theoil modified resin gave a clear bead on cooling which occurred in 15minutes. Volatiles were then removed by continued heating at the sametemperature under 28 inches of vacuum, and the resin mass thendischarged into pans to cool. A yield of 1020 parts of oil modifiedresin having a melting point of 96 C. was obtained.

Repeating this same example at high temper ature, with the exceptionthat the original acid catalyst was completely neutralized and the resinmass made slightly alkaline with barium hydroxide, it was found thatupon heating the raw soya bean oil and the resin to 300 C. incipientgelation of th reaction mass had begun before the oil had beencompletely dispersed; this required the immediate discharge of thereaction mass from the vessel.

A comparison of these examples clearly shows that the addition of moreacid to a Novolak resin that still has present in it the original acidcondensation catalyst, as in Example 1a, enables a fatty oil to beincorporated in a Novolak type resin with rapidity at moderatetemperatures or below 175 C.; in contrast the absence of added acidgreatly prolongs the reaction period at moderate temperatures as shownby Example 1b,

4 though with sufiicient amount of the ori inal acid present to give apH of 1.6 (0.95 per cent of phosphoric acid) the reaction proceeds in amanner to solubilize the oil in the resin without gelation and yields ahomogeneous product. A high temperature (300 C.) reaction as illustratedby Example 10, however, so speeds up the reaction at a pH of 1.6 thatgelation takes place substantially simultaneously with solubilization ofthe oil; and on the other hand complete neutralization (pH of more than8.25) in a high temperature reaction also is ineffective due to gelationof the resin before complete dispersal of the oil therein. From this theconclusion follows that a moderate reaction temperature (215 C. andbelow) does not have the limitations of a narrow pH range associatedwith high reaction temperatures (215 C. and above).

The following examples illustrate the use of other fatty oils indiffering proportions and with various phenol aldehyde resins and acidcatalysts.

Example 2.A base Novolak type resin, illustrating a higher formaldehydecontent (0.81 mol per mol of phenol) than that described in Example 1,was made by-reacting 5000 parts of phenol containing 10 per cent ofortho cresol with 3500 parts of 37% aqueous formaldehyde and with 50parts of 'per cent strength phosphoric acid as a catalyst; the mixturebefore reaction had a pH of 1.1-1.25. The mixture was refluxed in asteam heated vessel for six hours with continuous stirring until 96.3per cent of the formaldehyde had reacted and the pH value of theundehydrated resin was 1.6. The resin was dehydrated by heating underatmospheric pressure to C. and then discharged iromthe vessel; a yieldof 5500 parts of a resin having a melting point of 72 C. was obtainedwhich was used in the following subsidiary examples.

500 parts of the above Novolak resin were heated with 110 parts of blownsoya bean oil to a temperature of 170 C. in a steam heated vessel.

The mixture was at first cloudy but a clear head when cold was obtainedafter about 15 hours of reaction at -175 C. with constant stirring. Themodified oil-resin was heated under 28 inches of vacuum for one-halfhour at the same temperature to eliminate volatiles whereupon it wasdischarged into pans for cooling, and a sample of the cooled mass had amelting point of 111 C. With the same reactants and proportions asolubilize.- tion of the fatty oil into the Novolak resin in onetenththe time was secured when 15 parts of 85 per cent phosphoric acid (3% onthe weight of the Novolak resin) previously dissolved in alcohol wasadded to the melted Novolak resin and immediately followed with theaddition of the fatty oil; in this instance only one and one-half hoursreaction at 165 C. sufllced to incorporate the fatty oil into theNovolak resin, and 5 minutes of the vacuum treatment was sufficient togive a homogeneous oil modified resin which had a melting point of 107C. Since the oil-modified-resins tend to gel easily in the presenc ofsuch a quantity of acid, it'is preferable to neutralize the added acid,after the fatty oil is completely incorporated with any alkali whichwill form a stable salt with the acid; powdered slaked lime dispersed ina small amount of water is suitable for this purpose, and it is added tothe resin immediately after sclubilization of the oil has taken placeand prior to the vacuum treatment step.

With sulphuric acid a the solubilization catalyst, a lesser quantity isrequired than in the case of phosphoric acid. For instance, with 2 percent of sulphuric acid based on the weight of the Novolak type resin thesame reactants in the sam amounts gave a clear oil-modified resin inabout 15 minutes; the excess acid in the oil-modified resin was thenneutralized with a water dispersion of ground lime, and the water andother volatiles were removed by subjecting the resin to a vacuum of 28inches for minutes at a temperature of 170 C.

The resin of this example had a melting point of 112 C. and containedabout 20 per cent of incorporated oil.

Example 3.-Oil-modified resins containing blown grapefruit seed oil showthe decided impetus given to the solubilization of the oil intoRepeating this example with the addition of 2 per cent ofconcentrated'sulphurlc acid based on the Novolak resin enabled the oilto be completelydispersed in the resin after only 16 minutes of reactiontime at 150-165 C. The excess acid was then neutralized by adding aconcentrated aqueous solution of sodium hydroxide; dehydration of theoil modified resin and the removal of unreacted volatile matter wasaccomplished by heating for 5 minutes at 170 C. under a high vacuum. Theresin-was discharged into pans, and a sample showed a slightly highermelting point of 106 C.

Example 4.--High viscosity heat-bodied fatty oils are usually quitedifficult to incorporate into a Novolak resin; however when the Novolakresin is sufliciently acidified, these oils readily disperse themselvesin the resin at moderate temperatures.

500 parts of the base Novolak resin prepared for Example 2 and 110 partsof a heat-bodied linseed oil with a viscosity value of M17 (Gardner-Holdt scale) (which is sold under the trade name of 0K0 oil) werereacted together with 2 per cent of concentrated sulphuric acid at atemperature of 150 C. for 35 minutes to yield a clear homogeneouoil-modified resin. The excess acid present in the resin was neutralizedby the addition of an aqueous solution of barium hydroxide; the waterand other volatile matter in the resin was removed by heating the resinmass to 170 C. for 15 minutes under high vacuum, yielding a tained. Themass was preferably but not necessarily neutralized with 2.3 parts oflime dispersed in 5 parts of water whereupon a vacuum of 15 inches wasapplied for 10 minutes. The discharged resin had a melting point ofabout 100 C. Example 6.200 parts of the base resin of Example 5 wereheated to 150 C. and 8 parts of p-toluene sulphonic acid dissolved in 15parts of alcohol were added. The temperature was again brought up to 150C. and while stirring there were added 50 parts of alkali-refined fishoil. The mass was reacted for 16 minutes at 150-165.C. or until a clearbead when cold was obtained. The discharged resin had a melting point of110 C.

Example '7.200 parts of the base resin of Example 5 were treated as inExample 1 with 4 parts of concentrated sulphuric acid dissolved in 10parts of alcohol. For the oil there were substituted 50 parts ofdehydrated ca-stor oil. This mass gave a clear bead when heated for 12minutes at 150 C. and the resulting resin had a melting point of about100 C. p 7

Example 8.100 parts of the base resin of Example 5 were melted andraised to 150 C.; to this were added 4 parts of p-toluene sulphonic aciddissolved in 10 parts of alcohol and the temperature again brought to150 C. 67 parts of blown soya bean oil were added to the resin and themass reacted for 20 minutes at 150-160 C. or to a clear bead when cold.In this example the oil constituted about 40% based on the weight ofresin and the resin showed some tendency to gel in the removal ofvolatiles due to the presence of the excess acid; it is thereforepreferable in preparing high oil content resins to reduce the quantityof acid catalyst which is added. The

resin product had a melting point of about 103 C.

Example 9.-Instead of incorporating the acid catalyst in the resin itcan be first added to the oil and the resin thereupon included; thisprocedure is applicable more particularly to raw oils of lowunsaturation, since blown oils and oils with conjugated double bonds arelikely to gel upon mixing with the acid catalyst. To illustrate, partsof raw soya bean oil had added thereto 2 parts of concentrated sulphuricacid dissolved in at 160 C. with stirring it became homogeneous and aclear bead when cold was obtained. The

resin containing about 20 per cent of combined oil and with a meltingpoint of 105 C.

Example 5.A base resin of the Novolak type was prepared from 100 partsof phenol (derived from coal tar and containing 10% of ortho cresol) and70 parts of 37 aqueou formaldehyde in the presence of 1 part of 85%phosphoric acid; pure synthetic phenol can be substituted. 500 parts ofthe resin so prepared were heated to 150 C., and 3 parts of sulphuricacid dissolved in 10 parts of alcohol were added with stirring; thisamounted to 0.6% of sulphuric acid based on the weight of the resin.

The mass was again brought to a temperatur of 150 C. whereupon 125 partsof blown soya bean oil were added. The temperature was raised to 160-165C. and the reaction continued for 40-45 minutes or until a clear beadwhen cold was obmass was neutralized with 3.1 parts of lime in 5 partsof water and the heating was continued at 160 C. for 10 minutes. Thedischarged resin was clear and grindable.

Example 10.The acids of fatty oils, such as linseed oil fatty acids orfatty acids having 7 carbon atoms or more, can be substituted for thefatty oils. of Example 5 were treated with 2 parts of concentratedsulphuric acid in 10 parts of alcohol under the conditions of Example 5and then 25 parts of linseed oil fatty acids were incorporated. it wasfound that a reactionfor'5 minutes at 160-165 C. gave a very clear bead.The product ugor removal of volatiles had a. melting point of 8 Example11.Resins of a Novolak nature and suitable for the purposes of thisinvention can be prepared from dihydroxy phenols as well as themonohydroxy phenols provided the formaldehyde proportion is reduced. Asan example,

When parts of the Novolak resin 1500 parts of resorcinol were heated to120 C. and 551 parts of 37% aqueous formaldehyde (ratio of .5 molformaldehyde to 1 mol of resorcinol) were slowly added over a period of30-45 minutes; this mixture was refluxed for about 30 minutes or untilsubstantially all the formaldehyde was reacted. The resin mass wasdehydrated by heating to 150 C. and by the application of a 27 inchvacuum for '7 minutes. A yield of 1577 parts of resin resulted with amelting point of about 80 C.

Example 11a.-1000 parts of the resorcinol resin were melted, and 700parts of blown soya bean oil were incorporated with stirring. The masswas reacted for 3 hours at 215 C. with stirring and dehydrated undervacuum. The discharged resin was clear and grindable having a meltingpoint of 90 C.; it had an oil content of about 41 per cent.

Example 11b.1000 parts of the resorcinol resin were melted and 700 partsof blown soya bean oil added with stirring. To the mass were added 10parts of concentrated sulphuric acid dissolved in 40 parts of acetoneand the whole was reacted at 150 C. for several minutes or until clear.A 22 inch vacuum was applied for minutes and the resin was discharged.It had a melting point of 100 C.

Example 12.Hydrogenated fatty oils have been found to be well suited forthe preparation of oil-modified resins. 100 parts of the resin describedin Example 2 were melted, and 3 parts of sulphuric acid dissolved inparts of alcohol were included. The mixture was heated to 140 C.whereupon 25 parts of approximately 80% hydrogenated cotton seed oilwere incorporated with stirring. The mass was heated at 150 C. for about5 minutes and then raised to 160 C. with heating continued for about 20minutes under agitation. By this time the mass was clear andhomogeneous, and it was neutralized with 2.3 parts of lime dispersed in10 parts of water. It was again brought to a temperature of 160 C. andthe volatiles removed. The product had a melting point of 93 C. and wasfree from any cloudiness.

Example .13.-100 parts of the base Novolak resin of Example 5 weremelted and 4 parts dimethyl sulphate dissolved in 10 parts alcohol wereadded with stirring. The mixture was heated to 150 C., and 25 partsblown soya bean oil were added. The mixture was again heated to 150-160C. and reacted with stirring for min utes, after which a dark coloredbut clear bead was obtained. The final resinous product had a meltingpoint of 100 C. In this example it is believed that the dimethylsulphate methylates the resin, liberating H2804 which then acts as acatalyst.

In general the invention has application to resins of the Novolak orslowly heat-hardening types of resins, i. e., resins which when used asbinders in molding material do not harden by heat within a time rangeuseful commercially and require the addition of a hardening agent inamounts from 2-15 per cent to accelerate their heat-hardenability.Different phenols can be used to prepare the base Novolak resinincluding phenol proper, cresols and xylenols and dihydroxy phenols suchas resorcinol, catechol, hydroquinone, etc.; other alkyl and arylsubstituted phenols give resins whose solubilization in oils can bepromoted by the catalysts herein disclosed though as a rule the resinsmade therefrom are sufficiently oilsoluble without their addition. Thealdehydes 8 suitable for reaction with the phenols include formaldehyde,acetaldehyde. furfuraldehyde, etc., their polymers and compoundsengendering methylene groups such as hexamethylenetetramine; with themore highly substituted aidehydes, the resins may be sufficientlyoil-soluble without the catalyst. The proportion of aldehyde to phenolcan be varied from 0.5-0.7 mol per mol of dihydroxy phenols to 0.5-0.9mol per mol of phenol.

Fatty oils of various degrees of unsaturation including the knowndrying, semi-drying and non-drying oils of fish and vegetable origin,and processed oils, as the oxidized, heat-polymerized, hydrogenated,dehydrated, etc., can be solubilized in the resins in accordance withthis invention. In place of the oils their acids or fatty acids havingseven carbon atoms or more, such as caprylic, lauric, oleic, linoleic,etc., can be used. The heat-polymerized oils are particularly effectivein the preparation of resins used in compositions exposed to hightemperatures or requiring resistance to heat. The percentage of oil inthe oil-modified resin normally varies from 10 to 60 per cent when usedin molding compositions and the like; for other purposes as coatings andthe like more oil can be added depending upon flexibility or otherproperties desired.

Solubilizing catalysts comprise the hydrates of phosphorus pentoxide,sulfuric acid (including oleum) and its compounds such as organicsulfonic acids (as phenol-sulfonic, toluene-sulfonic,naphthalene-sulfonic), alkyl sulfuric acids (as ethyl sulfuric), halogensulfonicacids (as chlorsulfonic acid) and compounds which under re-*acting conditions liberate or form sulfuric acid or derivatives of theforegoing types such as S03, Ca(SO4).H2SO4, dimethyl sulfate, etc. Thesulphuric acid compounds are defined herein, as compounds of sulphurtrioxide having the empirical formula RSO:H wherein R is a radical fromthe group consisting of halogen, hydroxyl, alkyl, aryl, and -OX whereinX is an alkyl radical. Under this formula it is intended to include theforegoing compounds when liberated or formed under the reactionconditions. The quantity of catalyst used in general varies from 0.1 to4.0 per cent calculated as phosphoric or sulfuric acid on the weight ofresin; higher percentages can be used with corresponding danger ofpremature gelation especially at temperatures ranging from 150-215 C.,but they are tolerated when the reaction temperatures are within therange of -150 C.

Oil-modified resins as herein described find particular utility, whencombined with hardening agents, such as hexamethylenetetramine and othermethylene-bearing compounds, as binders for fillers in moldingmaterials, brake linings, grinding wheels, etc. They are useful asheatsetting adhesives in the manufacture of plywood and also forcoatings; for these uses the hardening agent need not necessarily beincluded particularly if the catalytic acid is not neutralized.

What is claimed is:

1. Process of preparing an oil-modified resinous composition whichcomprises reacting at a temperature ranging from 115 C. to 215 C. anormally oil-insoluble, dehydrated Novolak phenol-aldehyde resin with afatty material selected from the group consisting of raw fatty oils,oxidized fatty oils, heat-polymerized fatty oils, dehydrated fatty oils.hydrogenated fatty oils and fatty acids having at least 7 carbon atomsand in the presence of an acidic catalyst selected fromv the groupconsisting of the hydrates of phosphorus pentoxide, dialkyl sulphates,

Ca(SO4) .H2SO4 sulphur trioxide and its compounds having the formulaRSO3H whereinR is a radical selected from the group consisting ofhalogen, hydroxyl and aryl radicals and OX wherein X i: an alkylradical, said catalyst calculated as phosphoric acid or sulphuric acidbeing present in amount between 0.1 and 4.0 percent by weight of theNovolak resin.

2. Process of preparing an oil-modified resinous composition whichcomprises reacting at a temperature ranging from 130 C. to 175 C. anormally oil-insoluble, dehydrated Novolak phenol-aldehyde resin with afatty material selected from the group consisting of raw fatty oils,oxidized fatty oils, heat polymerized fatty oils, dehydrated fatty oils,hydrogenated fatty oils and fatty acids having at least 7 carbon atomsand in the presence of an acidic catalyst selected from the groupconsisting of the hydrates of phosphorus pentoxide, dialkyl sulphates,

CMSOO .H2SO4 sulphur trioxide and its compounds having the formulaR-SO:H wherein R is a radical selected from the group consisting ofhalogen, hydroxyl and aryl radicals and --OX wherein X is an alkylradical, said catalyst calculated as phosphoric acid or sulphuric acidbeing present in amount between 0.1 and 4.0 percent by weight of theNovolak resin.

3. Process of preparing an oil-modified resinous composition whichcomprises reacting at a temperature ranging from 115 C. to 215 C. anormally oil-insoluble, dehydrated Novolak phenol-aldehyde resin with afatty material selected from the group consisting of raw fatty oils,oxidized fatty oils, heat-polymerized fatty oils, dehydrated fatty oils,hydrogenated fatty oils and fatty acids having at least '7 carbon atoms,said fatty material comprising between 10 and 60 percent of the weightof the modified resin and said reaction being conducted in the presenceof a catalyst selected from the group consisting of the hydrates ofphosphorus pentoxide, dialkylsulphates, Ca.(SO4).H2SO4, sulphur trioxideand its compounds having the formulaR-SOaH wherein R is a radicalselected from the group consisting 10 of halogen, hydroxyl and arylradicals and OX wherein X is an alkyl radical, said catalyst calculatedas phosphoric acid or sulphuric acid being present in amount between 0.1and 4.0 percent by weight of the Novolak resin.

4. Process of preparing an oil-modified resinous composition whichcomprises reacting at a temperature between C. and 215 C. a normallyoil-insoluble, dehydrated Novolak resin prepared from a phenol which inpart is unsubstituted phenol and with less than a mol of formaldehydefor each mol of ,phenol with a fatty material selected from the groupconsisting of raw fatty oils, oxidized fatty oils, heat-polymerizedfatty oils, dehydrated fatty oils, hydrogenated fatty oils and fattyacids having at least 7 carbon atoms, and in the presence of an acidiccatalyst selected from the group consisting of the hydrates ofphosphorus pentoxide, dialkyl sulphates, Ca(SO4).H 2SO4, sulphurtrioxide and its compounds having the formula RSO:H wherein R is aradical selected from the group consisting of halogen, hydroxyl and arylradicals and OX wherein X is an alkyl radical, said catalyst calculatedas phosphoric acid or sulphuric acid being present in amount between 0.1and 4.0 percent by weight of the Novolak resin.

5. Process of preparing an oil-modified resinous composition whichcomprises reacting at a temperature between 115 C. and 215 C. a normallyoil-insoluble, dehydrated Novolak phenolaldehyde resin with a fattymaterial selected from the group consisting of raw fatty oils, oxidizedfatty oils, heat-polymerized fatty oils, dehydrated fatty oils,hydrogenated fatty oils and fatty acids having at least 7 carbon atomsand in the presence of an acidic catalyst selected from the groupconsisting of the hydrates of phosphorus pentoxide, dialkyl sulphates,Ca(SO4) .H2SO4, sulphur trioxide and its compounds having the formulaRSO3H wherein R is a radical selected from the group consisting ofhalogen, hydroxyl and aryl radicals and --OX wherein X is an alkylradical, said catalyst calculated as phosphoric acid or sulphuric acidbeing present in amount between 0.1

and 4.0 percent by weight of the Novolak resin,

and then neutralizing the acidic catalyst with an alkali that forms astable salt with the acidic catalyst after the fattymaterial has reactedwith the Siovolak resin.

ARTHUR P. MAZZUCCHELLI.

